pk a Values for Selected Compounds

Transcription

1 Appendix A pk a Values for Selected ompounds ompound pk a ompound pk a I 10 Br 9 2 S S 3 7 Br N l 7 [( 3 ) 2 ] [ 3 2 ] S N2 0.0 F l N l P F l Br I F N N ( 3 ) N N + N S N 7.1 S Br + N A-1

2 Appendix A pk a Values for Selected ompounds A-2 ompound pk a ompound pk a N 9.1 l N N N N S 10.5 [( 3 ) 3 N] Et 10.7 [ 3 N 3 ] N [( 3 ) 2 N 2 ] F N ( 3 ) 3 18 ( 3 ) N 25 l N( 3 ) N N Et Et

3 Appendix B Nomenclature Although the basic principles of nomenclature are presented in the body of this text, additional information is often needed to name many complex organic compounds. Appendix B concentrates on three topics: Naming alkyl substituents that contain branching Naming polyfunctional compounds Naming bicyclic compounds Naming Alkyl Substituents That ontain Branching Alkyl groups that contain any number of carbons and no branches are named as described in Section 4.4A: change the -ane ending of the parent alkane to the suffix -yl. Thus the seven-carbon alkyl group is called heptyl. When an alkyl substituent also contains branching, follow a stepwise procedure: [1] Identify the longest carbon chain of the alkyl group that begins at the point of attachment to the parent. Begin numbering at the point of attachment and use the suffix -yl to indicate an alkyl group Start numbering here. 4 s in the chain butyl group Start numbering here. 5 s in the chain pentyl group [2] Name all branches off the main alkyl chain and use the numbers from Step [1] to designate their location. methyl group at 3 methyl groups at 1 and methylbutyl 1,3-dimethylpentyl A-3

4 Appendix B Nomenclature A-4 [3] Set the entire name of the substituent in parentheses, and alphabetize this substituent name by the first letter of the complete name. 1 of the six-membered ring (3-methylbutyl)cyclohexane 1-(1,3-dimethylpentyl)-2-methylcyclohexane Alphabetize the d of dimethylpentyl before the m of methyl. Number the ring to give the lower number to the first substituent alphabetically: place the dimethylpentyl group at 1. Naming Polyfunctional ompounds Many organic compounds contain more than one functional group. When one of those functional groups is halo (X ) or alkoxy ( ), these groups are named as substituents as described in Sections 7.2 and 9.3B. To name other polyfunctional compounds, we must learn which functional group is assigned a higher priority in the rules of nomenclature. Two steps are usually needed: [1] Name a compound using the suffix of the highest priority group, and name other functional groups as substituents. Table B.1 lists the common functional groups in order of decreasing priority, as well as the prefixes needed when a functional group must be named as a substituent. [2] Number the carbon chain to give the lower number to the highest priority functional group, and then follow all other rules of nomenclature. Examples are shown in Figure B.1. Polyfunctional compounds that contain double and triple bonds have characteristic suffixes to identify them, as shown in Table B.2. The higher priority functional group is assigned the lower number. Table B.1 Summary of Functional Group Nomenclature Functional group Suffix Substituent name (prefix) Increasing priority arboxylic acid -oic acid carboxy Ester -oate alkoxycarbonyl Amide -amide amido Nitrile -nitrile cyano Aldehyde -al oxo ( ) or formyl ( ) Ketone -one oxo Alcohol -ol hydroxy Amine -amine amino Alkene -ene alkenyl Alkyne -yne alkynyl Alkane -ane alkyl Ether alkoxy alide halo

5 A-5 Appendix B Nomenclature Figure B.1 Examples of nomenclature of polyfunctional compounds N highest priority 3-amino-2-hydroxybutanal Name as a derivative of an aldehyde since is the highest priority functional group. N higher priority o-cyanobenzoic acid Name as a derivative of benzoic acid since is the higher priority functional group higher priority methyl 4-oxohexanoate Name as a derivative of an ester since is the higher priority functional group. N 2 highest priority 3 4-formyl-3-methoxycyclohexanecarboxamide Name as a derivative of an amide since N 2 is the highest priority functional group. Table B.2 Naming Polyfunctional ompounds with Double and Triple Bonds Functional groups Suffix Example and enol Start numbering here. 5-methyl-4-hexen-1-ol + (ketone) enone Start numbering here. (4E)-4-hepten-3-one + enyne Start numbering here hexen-5-yne Naming Bicyclic ompounds Bicyclic ring systems compounds that contain two rings that share one or two carbon atoms can be bridged, fused, or spiro. bridged ring fused ring spiro ring A bridged ring system contains two rings that share two non-adjacent carbons. A fused ring system contains two rings that share a common carbon carbon bond. A spiro ring system contains two rings that share one carbon atom.

6 Appendix B Nomenclature A-6 Fused and bridged ring systems are named as bicyclo[x.y.z]alkanes, where the parent alkane corresponds to the total number of carbons in both rings. The numbers x, y, and z refer to the number of carbons that join the shared carbons together, written in order of decreasing size. For a fused ring system, z always equals zero, because the two shared carbons are directly joined together. The shared carbons in a bridged ring system are called the bridgehead carbons. 1 joining the bridgehead s 8 s in the ring system bicyclooctane 3 s joining the bridgehead s 2 s joining the bridgehead s Name: bicyclo[3.2.1]octane 10 s in the ring system bicyclodecane 4 s joining the common s Name: bicyclo[4.4.0]decane 4 s joining the common s No s join the shared s at the ring fusion. ings are numbered beginning at a shared carbon, and continuing around the longest bridge first, then the next longest, and so forth. 6 8 Start numbering here Start numbering here ,3-dimethylbicyclo[3.2.1]octane 7,7-dimethylbicyclo[2.2.1]heptane Spiro ring systems are named as spiro[x.y]alkanes where the parent alkane corresponds to the total number of carbons in both rings, and x and y refer to the number of carbons that join the shared carbon (the spiro carbon), written in order of increasing size. When substituents are present, the rings are numbered beginning with a carbon adjacent to the spiro carbon in the smaller ring Start numbering here s in the ring system 8 s in the ring system Name: spiro[4.5]decane Name: 2-methylspiro[3.4]octane

7 Appendix Bond Dissociation Energies for Some ommon Bonds [A B A + B] Bond o kj/mol (kcal/mol) Z bonds F 569 (136) l 431 (103) Br 368 (88) I 297 (71) 498 (119) Z Z bonds 435 (104) F F 159 (38) l l 242 (58) Br Br 192 (46) I I 151 (36) 213 (51) bonds (104) (98) (98) ( 3 ) (95) ( 3 ) (91) (104) 523 (125) (87) (110) (85) bonds (88) (85) (92) (117) A-7

8 Appendix Bond Dissociation Energies for Some ommon Bonds [A B A + B] A-8 Bond o kj/mol (kcal/mol) X bonds 3 F 456 (109) 3 l 351 (84) 3 Br 293 (70) 3 I 234 (56) 3 2 F 448 (107) 3 2 l 339 (81) 3 2 Br 285 (68) 3 2 I 222 (53) ( 3 ) 2 F 444 (106) ( 3 ) 2 l 335 (80) ( 3 ) 2 Br 285 (68) ( 3 ) 2 I 222 (53) ( 3 ) 3 F 444 (106) ( 3 ) 3 l 331 (79) ( 3 ) 3 Br 272 (65) ( 3 ) 3 I 209 (50) bonds (93) (94) (92) ( 3 ) (96) ( 3 ) (96) ther bonds (152) 837 (200) 535 (128) (119)

9 Appendix D eactions That Form arbon arbon Bonds Section eaction 11.11A S N 2 reaction of an alkyl halide with an acetylide anion, 11.11B pening of an epoxide ring with an acetylide anion, adical polymerization of an alkene Diels Alder reaction 18.5 Friedel rafts alkylation 18.5 Friedel rafts acylation eaction of an aldehyde or ketone with a Grignard or organolithium reagent 20.13A eaction of an acid chloride with a Grignard or organolithium reagent 20.13A eaction of an ester with a Grignard or organolithium reagent 20.13B eaction of an acid chloride with an organocuprate reagent A A eaction of a Grignard reagent with B eaction of an epoxide with an organometallic reagent eaction of an α,β-unsaturated carbonyl compound with an organocuprate reagent 21.9 yanohydrin formation Wittig reaction to form an alkene S N 2 reaction of an alkyl halide with NaN eaction of a nitrile with a Grignard or organolithium reagent 23.8 Direct enolate alkylation using LDA and an alkyl halide 23.9 Malonic ester synthesis to form a carboxylic acid Acetoacetic ester synthesis to form a ketone 24.1 Aldol reaction to form a β-hydroxy carbonyl compound or an α,β-unsaturated carbonyl compound 24.2 rossed aldol reaction 24.3 Directed aldol reaction 24.5 laisen reaction to form a β-keto ester 24.6 rossed laisen reaction to form a β-dicarbonyl compound 24.7 Dieckmann reaction to form a five- or six-membered ring 24.8 Michael reaction to form a 1,5-dicarbonyl compound 24.9 obinson annulation to form a 2-cyclohexenone eaction of a diazonium salt with un 26.1 oupling of an organocuprate reagent ( 2 uli) with an organic halide ('X) 26.2 The palladium-catalyzed Suzuki reaction of an organic halide with an organoborane 26.3 The palladium-catalyzed eck reaction of a vinyl or aryl halide with an alkene 26.4 Addition of a dihalocarbene to an alkene to form a cyclopropane 26.5 Simmons Smith reaction of an alkene with 2 I 2 and Zn(u) to form a cyclopropane 26.6 lefin metathesis 27.10B Kiliani Fischer synthesis of an aldose 28.2B Alkylation of diethyl acetamidomalonate to form an amino acid 28.2 Strecker synthesis of an amino acid 30.2 hain-growth polymerization 30.4 Polymerization using Ziegler Natta catalysts

10 Alkene 1650 medium haracteristic I Absorption Frequencies Appendix E Bond Functional group Wavenumber (cm 1 ) omment N broad, strong very broad, strong N two peaks 2 N one peak N 2, N one or two peaks; N bending also observed at 1640 cm 1 sp 3300 sharp, often strong sp medium sp strong sp 2 of one or two peaks 2250 medium N 2250 medium strong l 1800 () , 1760 two peaks increasing ν ~ with decreasing ring size increasing ν ~ with decreasing ring size 2, conjugated N 2, N, increasing ν ~ with decreasing N 2 ring size Arene 1600, 1500 medium N 1650 medium A-10

11 Appendix F haracteristic NM Absorptions 1 NM Absorptions ompound type hemical shift (ppm) Alcohol Aldehyde 9 10 Alkane ~ ~1.3 3 ~1.7 Alkene sp allylic sp Alkyl halide F l Br I A-11 Alkyne ~2.5

12 ompound type hemical shift (ppm) Amide N Amine N N Aromatic compound sp benzylic sp arbonyl compound sp 3 on the α carbon arboxylic acid Ether NM Absorptions arbon type Structure hemical shift (ppm) Alkyl, sp 3 hybridized 5 45 Alkyl, sp 3 hybridized bonded to N,, or X Alkynyl, sp hybridized Z Z = N,, X Alkenyl, sp 2 hybridized Aryl, sp 2 hybridized arbonyl A-12

13 Appendix G General Types of rganic eactions Substitution eactions [1] Nucleophilic substitution at an sp 3 hybridized carbon atom a. Alkyl halides (hapter 7) X + Nu nucleophile Nu + X b. Alcohols (Section 9.11) + X X + 2 c. Ethers (Section 9.14) ' + X X + ' X + 2 X = Br or I [1] Nu [2] 2 d. Epoxides (Section 9.15) or Z Nu Nu or Z = nucleophile (Z) [2] Nucleophilic acyl substitution at an sp 2 hybridized carbon atom arboxylic acids and their derivatives (hapter 22) Z + Nu nucleophile Nu + Z Z =, l,, ', N' 2 [3] adical substitution at an sp 3 hybridized bond Alkanes (Section 15.3) + X 2 hν or X + X [4] Electrophilic aromatic substitution Aromatic compounds (hapter 18) + E + electrophile E + + A-13

14 Elimination eactions a Elimination at an sp 3 hybridized carbon atom Appendix G General Types of rganic eactions A-14 a. Alkyl halides (hapter 8) X + B base new π bond + + X B + b. Alcohols (Section 9.8) A new π bond + 2 Addition eactions [1] Electrophilic addition to carbon carbon multiple bonds a. Alkenes (hapter 10) b. Alkynes (Section 11.6) + X Y X Y X Y + X Y X Y [2] Nucleophilic addition to carbon oxygen multiple bonds Aldehydes and ketones (hapter 21) (') + Nu nucleophile 2 (') Nu

15 Appendix ow to Synthesize Particular Functional Groups Acetals eaction of an aldehyde or ketone with two equivalents of an alcohol (21.14) Acid chlorides eaction of a carboxylic acid with thionyl chloride (22.10) Alcohols Nucleophilic substitution of an alkyl halide with or 2 (9.6) ydration of an alkene (10.12) ydroboration oxidation of an alkene (10.16) eduction of an epoxide with LiAl 4 (12.6) eduction of an aldehyde or ketone (20.4) ydrogenation of an α,β-unsaturated carbonyl compound with 2 + Pd- (20.4) Enantioselective reduction of an aldehyde or ketone with the chiral BS reagent (20.6) eduction of an acid chloride with LiAl 4 (20.7) eduction of an ester with LiAl 4 (20.7) eduction of a carboxylic acid with LiAl 4 (20.7) eaction of an aldehyde or ketone with a Grignard or organolithium reagent (20.10) eaction of an acid chloride with a Grignard or organolithium reagent (20.13) eaction of an ester with a Grignard or organolithium reagent (20.13) eaction of an organometallic reagent with an epoxide (20.14B) Aldehydes ydroboration oxidation of a terminal alkyne (11.10) xidative cleavage of an alkene with 3 followed by Zn or ( 3 ) 2 S (12.10) xidation of a 1 alcohol with P (12.12) xidation of a 1 alcohol with r 4, Amberlyst A-26 resin (12.13) eduction of an acid chloride with LiAl[( 3 ) 3 ] 3 (20.7) eduction of an ester with DIBAL- (20.7) ydrolysis of an acetal (21.14B) ydrolysis of an imine or enamine (21.12B) eduction of a nitrile (22.18B) Alkanes atalytic hydrogenation of an alkene with 2 + Pd- (12.3) atalytic hydrogenation of an alkyne with two equivalents of 2 + Pd- (12.5A) eduction of an alkyl halide with LiAl 4 (12.6) A-15

16 Appendix ow to Synthesize Particular Functional Groups A-16 eduction of a ketone to a methylene group ( 2 ) the Wolff Kishner or lemmensen reaction (18.14B) Protonation of an organometallic reagent with 2,, or acid (20.9) oupling of an organocuprate reagent ( 2 uli) with an alkyl halide, 'X (26.1) Simmons Smith reaction of an alkene with 2 I 2 and Zn(u) to form a cyclopropane (26.5) Alkenes Dehydrohalogenation of an alkyl halide with base (8.3) Dehydration of an alcohol with acid (9.8) Dehydration of an alcohol using Pl 3 and pyridine (9.10) β Elimination of an alkyl tosylate with base (9.13) atalytic hydrogenation of an alkyne with 2 + Lindlar catalyst to form a cis alkene (12.5B) Dissolving metal reduction of an alkyne with Na, N 3 to form a trans alkene (12.5) Wittig reaction (21.10) β Elimination of an α-halo carbonyl compound with Li 2 3, LiBr, and DMF (23.7) ofmann elimination of an amine (25.12) oupling of an organocuprate reagent ( 2 uli) with an organic halide, 'X (26.1) The palladium-catalyzed Suzuki reaction of a vinyl or aryl halide with a vinyl- or arylborane (26.2) The palladium-catalyzed eck reaction of a vinyl or aryl halide with an alkene (26.3) lefin metathesis (26.6) Alkyl halides eaction of an alcohol with X (9.11) eaction of an alcohol with Sl 2 or PBr 3 (9.12) leavage of an ether with Br or I (9.14) ydrohalogenation of an alkene with X (10.9) alogenation of an alkene with X 2 (10.13) ydrohalogenation of an alkyne with two equivalents of X (11.7) alogenation of an alkyne with two equivalents of X 2 (11.8) adical halogenation of an alkane (15.3) adical halogenation at an allylic carbon (15.10) adical addition of Br to an alkene (15.13) Electrophilic addition of X to a 1,3-diene (16.10) adical halogenation of an alkyl benzene (18.13) alogenation α to a carbonyl group (23.7) Addition of a dihalocarbene to an alkene to form a dihalocyclopropane (26.4) Alkynes Dehydrohalogenation of an alkyl dihalide with base (11.5) S N 2 reaction of an alkyl halide with an acetylide anion, (11.11) Amides eaction of an acid chloride with N 3 or an amine (22.8) eaction of an anhydride with N 3 or an amine (22.9) eaction of a carboxylic acid with N 3 or an amine and D (22.10) eaction of an ester with N 3 or an amine (22.11)

17 A-17 Appendix ow to Synthesize Particular Functional Groups Amines eduction of a nitro group (18.14) eduction of an amide with LiAl 4 (20.7B) eduction of a nitrile (22.18B) S N 2 reaction using N 3 or an amine (25.7A) Gabriel synthesis (25.7A) eductive amination of an aldehyde or ketone (25.7) Amino acids S N 2 reaction of an α-halo carboxylic acid with excess N 3 (28.2A) Alkylation of diethyl acetamidomalonate (28.2B) Strecker synthesis (28.2) Enantioselective hydrogenation using a chiral catalyst (28.4) Anhydrides eaction of an acid chloride with a carboxylate anion (22.8) Dehydration of a dicarboxylic acid (22.10) Aryl halides alogenation of benzene with X 2 + FeX 3 (18.3) eaction of a diazonium salt with ul, ubr, BF 4, NaI, or KI (25.14A) arboxylic acids xidative cleavage of an alkyne with ozone (12.11) xidation of a 1 alcohol with r 3 (or a similar r 6+ reagent), 2, 2 S 4 (12.12B) xidation of an alkyl benzene with KMn 4 (18.14A) xidation of an aldehyde (20.8) eaction of a Grignard reagent with 2 (20.14A) ydrolysis of a cyanohydrin (21.9) ydrolysis of an acid chloride (22.8) ydrolysis of an anhydride (22.9) ydrolysis of an ester (22.11) ydrolysis of an amide (22.13) ydrolysis of a nitrile (22.18A) Malonic ester synthesis (23.9) yanohydrins Addition of N to an aldehyde or ketone (21.9) 1,2-Diols Anti dihydroxylation of an alkene with a peroxyacid, followed by ring opening with or 2 (12.9A) Syn dihydroxylation of an alkene with KMn 4 or s 4 (12.9B) Enamines eaction of an aldehyde or ketone with a 2 amine (21.12) Epoxides Intramolecular S N 2 reaction of a halohydrin using base (9.6) Epoxidation of an alkene with mpba (12.8) Enantioselective epoxidation of an allylic alcohol with the Sharpless reagent (12.15)

18 Appendix ow to Synthesize Particular Functional Groups A-18 Esters S N 2 reaction of an alkyl halide with a carboxylate anion, (7.19) eaction of an acid chloride with an alcohol (22.8) eaction of an anhydride with an alcohol (22.9) Fischer esterification of a carboxylic acid with an alcohol (22.10) Ethers Williamson ether synthesis S N 2 reaction of an alkyl halide with an alkoxide, (9.6) eaction of an alkyl tosylate with an alkoxide, (9.13) Addition of an alcohol to an alkene in the presence of acid (10.12) Anionic polymerization of epoxides to form polyethers (30.3) alohydrins eaction of an epoxide with X (9.15) Addition of X and to an alkene (10.15) Imine eaction of an aldehyde or ketone with a 1 amine (21.11) Ketones ydration of an alkyne with 2, 2 S 4, and gs 4 (11.9) xidative cleavage of an alkene with 3 followed by Zn or ( 3 ) 2 S (12.10) xidation of a 2 alcohol with any r 6+ reagent (12.12, 12.13) Friedel rafts acylation (18.5) eaction of an acid chloride with an organocuprate reagent (20.13) ydrolysis of an imine or enamine (21.12B) ydrolysis of an acetal (21.14B) eaction of a nitrile with a Grignard or organolithium reagent (22.18) Acetoacetic ester synthesis (23.10) Nitriles S N 2 reaction of an alkyl halide with NaN (7.19, 22.18) eaction of an aryl diazonium salt with un (25.14A) Phenols eaction of an aryl diazonium salt with 2 (25.14A)